Insecticidal substituted and unsubstituted benzoic acid 1-alkyl, 2-alkyl and 2-cycloalkylhydrazides

ABSTRACT

The present invention relates to methods for controlling insect populations and for protecting living plants from insect attack by applying to said plants or to the soil in which they are growing an insecticidally-effective amount of a substituted benzoic acid 1 or 2-alkyl or 2-cycloalkylhydrazide. 
     Novel substituted benzoic acid 1 and 2-alkyl and 2-cycloalkylhydrazides effective as insecticides or intermediates for the preparation of insecticidal diacylhydrazides also are presented.

BACKGROUND OF THE INVENTION

This application is a continuation of U.S. application Ser. No. 298,713,filed Jan. 19, 1989, now abandoned, which is a divisional of U.S.application Ser. No. 926,780, filed Nov. 12, 1986, now U.S. Pat. No.4,814,349, which is a continuation-in-part of U.S. Pat. application Ser.No. 806,981 filed Dec. 9, 1985, now abandoned.

The present invention relates to compounds which are usefulintermediates in the processing of dibenzoylhydrazines. Thesedibenzoylhydrazines are effective insecticidal stomach poisons and alsoare effective systemically in protecting living plants.

Further, the compounds of the invention are effective as insecticidesthemselves. These novel compounds and others have been found to controlinsects and protect living plants from insect attack.

Thus, it is an object of the present invention to provide these methodsfor controlling insect pests and protecting living plants through anextended period of active growth from insects which infest said livingplants.

It is another object of the invention to provide novel substitutedbenzoic acid 1-alkyl-, 2-alkyl- and 2-cycloalkylhydrazides, preferably 1or 2-tert-butylhydrazides, as insecticides and also to provide many ofsaid compounds useful in the preparation of dibenzoylhydrazineinsecticides.

These and further objects of the invention will become apparent by thefollowing more detailed description of the invention.

SUMMARY OF THE INVENTION

The present invention relates to a method for controlling insects andprotecting living plants from insect attack by applying to the foodsupply of said insects, including living plants upon which said insectsfeed, or the insects' breeding grounds or habitat, aninsecticidally-effective amount of a compound depicted by formula (I):##STR1## wherein R and R₆ are each independently hydrogen, C₂ -C₆ alkylor C₅ -C₆ cycloalkyl; X and Y are each independently H, C₁ -C₃ alkyl, C₁-C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF₃, R₁ CF₂ Z--,1,1-difluoro-2,2-dichloroethoxy, R₂ CO or R₃ R₄ N and when takentogether X and Y may form a ring in which XY are represented by thestructure: ##STR2## Z is S(O)n or O; R₁ is H, F, CHF₂, CHFCl or CF₃ ; R₂is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or R₃ R₄ N; R₃ is H or C₁ C₃ alkyl; R₄ isH, C₁ -C₃ alkyl or R₅ CO; R₅ is H or C₁ -C₃ alkyl and n is 0, 1 or 2;with the provisos that when R is hydrogen, R₆ is C₂ -C₅ alkyl or C₅ -C₆cycloalkyl and when R₆ is hydrogen, R is C₂ -C₅ alkyl or C₅ -C₆cycloalkyl.

A preferred group of compounds of the present invention include formula(I) compounds wherein R is tert-butyl, R₆ is hydrogen and X and Y are asdescribed hereinabove.

Another group of preferred compounds of the present invention includeformula (I) compounds wherein R is hydrogen, R₆ is tert-butyl and X andY are as described hereinabove.

The present invention also relates to novel substituted benzoic acid1-alkyl-, 2-alkyl- and 2-cycloalkylhydrazides, effective asinsecticides, having the structure depicted by formula (II): ##STR3##wherein R and R₆ are each independently hydrogen, C₂ -C₆ alkyl or C₅ -C₆cycloalkyl; X and Y are each independently H, C₁ -C₃ alkyl, C₁ -C₃alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃ alkylsulfonyl,cyano, F, Cl, Br, I, nitro, CF₃, R₁ CF₂ Z--,1,1-difluoro-2,2-dichloroethoxy, R₂ CO or R₃ R₄ N and when takentogether X and Y may form a ring in which XY are represented by thestructure: ##STR4## Z is S(O)n or O; R₁ is H, F, CHF₂, CHFCl or CF₃ ; R₂is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or R₃ R₄ N; R₃ is H or C₁ -C₃ alkyl; R₄is H, C₁ -C₃ alkyl or R₅ CO; R₅ is H or C₁ -C₃ alkyl and n is 0, 1 or 2;with the provisos that when R is hydrogen, R₆ is C₂ -C₅ alkyl or C₅ -C₆cycloalkyl and when R₆ is hydrogen, R is C₂ -C₅ alkyl or C₅ -C₆cycloalkyl; and provided also that when R is tert-butyl and Y is chloroin the para position of the ring, X is a substituent other thenhydrogen.

The novel substituted formula (II) benzoic acid 1-alkyl-, 2-alkyl- and2-cycloalkylhydrazides, like the formula (I), 1-alkyl-, 2-alkyl- and2-cycloalkylhydrazides, are potent stomach poisons. As such, theseformula (I) and formula (II) hydrazides effectively control insectpopulations and protect plants from insect attack.Insecticidally-effective amounts of the active compound can be appliedto the foliage of plants upon which the insects feed or to the soil,water or other media in which said plants are growing. These compoundsmay also be made available to the insects in the form of baits orapplied to the insects' breeding grounds and habitat.

Additionally, many of the novel formula (II) benzoic acid 1-alkyl-,2-alkyl- and 2-cycloalkylhydrazides, substituted with halogen, CH₃, CF₃,--OCH₃, --OCH₂ O--, OCF₂ O--, NH₂, NO₂ or --CH═CH--CH═CH--, are usefulas intermediates for the preparation of dibenzoylhydrazines which areeffective as insecticidal agents and systemic soil insecticidal agents.

DETAILED DESCRIPTION OF THE INVENTION Process of Manufacture

The formula (I) benzoic acid 1-alkyl-, 2-alkyl- and2-cycloalkylhydrazides of the present invention are depicted by thefollowing structure: ##STR5## wherein R and R₆ are each independentlyhydrogen, C₂ -C₆ alkyl or C₅ -C₆ cycloalkyl; X and Y are eachindependently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF₃, R₁CF₂ Z--, 1,1-difluoro-2,2-dichloroethoxy, R₂ CO or R₃ R₄ N and whentaken together X and Y may form a ring in which XY are represented bythe structure: ##STR6## Z is S(O)n or O; R₁ is H, F, CHF₂, CHFCl or CF₃; R₂ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or R₃ R₄ N; R₃ is H or C₁ -C₃ alkyl;R₄ is H, C₁ -C₃ alkyl or R₅ CO; R₅ is H or C₁ -C₃ alkyl and n is 0, 1 or2; with the provisos that when R is hydrogen, R₂ is C₂ -C₅ alkyl or C₅-C₆ cycloalkyl and when R₆ is hydrogen, R is C₂ -C₅ alkyl or C₅ -C₆cycloalkyl.

The formula (I) 2-alkyl- and 2-cycloalkylhydrazides of the invention areprepared by reacting an alkyl- or cycloalkylhydrazine hydrohalide with abenzoylhalide in the presence of aqueous base.

Generally, the alkyl or cycloalkylhydrazine hydrohalide is dispersed inan organic solvent, such as methylene chloride, ether or the like, andthe resulting mixture then admixed with aqueous base. Usually, about twoto six molar equivalents of base, such as sodium carbonate or sodiumhydroxide, per equivalent of alkylhydrazine hydrohalide are used toachieve the benzoylation of the alkyl hydrazine. The thus-preparedmixture is then admixed with the appropriate benzoyl halide dissolved ordispersed in an organic solvent, preferably the same solvent used fordissolution of the alkyl- or cycloalkyl- hydrazine hydrohalide.

The mixture is stirred or agitated for a sufficient period of time toform the benzoic acid alkyl- cycloalkylhydrazide which is readilyrecovered from the mixture by separation of the aqueous phase from theorganic phase and evaporation of the organic solvent from said organicphase.

The reaction is graphically illustrated below: ##STR7## wherein Q ishalogen, preferably chlorine and R, X and Y are as described for formula(I) compounds illustrated hereinabove.

The formula (I) benzoic acid, 1-alkyl and 2-cycloalkylhydrazides of thisinvention, depicted by the structure: ##STR8## wherein R is hydrogen; R₆is C₂ -C₆ alkyl or C₅ -C₆ cycloalkyl and X and Y are as describedhereinabove, are prepared by reacting an alkylhydrazine orcycloalkylhydrazine with acetone. After the mixture is permitted tostand for a short period of time, it is treated with ether and potassiumhydroxide pellets. The ether layer is separated from the mixture andevaporated to yield the 1-alkyl-2-isopropylidenehydrazide or1-cycloalkyl-2-isopropylidenehydrazide.

The resulting 1-alkyl- or 1-cycloalkyl-2-isopropylidene hydrazide thenis reacted with a benzoyl halide in the presence of 10% sodium hydroxideto yield 1-alkyl or 1-cycloalkyl 2-isopropylidenehydrazide of benzoicacid. Hydrolysis of the thus-formed product with a dilute mineral acidsuch as 10% HCl in the presence of alcohol yields the 1-alkyl or1-cycloalkylhydrazide of benzoic acid.

These reactions are illustrated as follows: ##STR9## wherein R₆, X and Yare as described hereinabove.

Preparation of the formula (I) benzoic acid alkyl- andcycloalkylhydrazides of this invention, wherein R₆ is hydrogen, also isachieved by reduction of the appropriate benzoic acid alkylidenehydrazide with hydrogen in the presence of a noble metal catalyst, suchas platinum or palladium. The reaction preferably is conducted in thepresence of a lower alkyl (C₁ -C₄) alcohol under a blanket of hydrogenmaintained at about 20 to 60 psig. The reaction is illustrated below:##STR10## wherein R₁, X and Y are as described for formula (I) compoundshereinabove.

Formula (I) benzoic acid 2-alkylhydrazides and 2-cycloalkylhydrazidesare useful as intermediates for the preparation of dibenzoylhydrazinecompounds illustrated by formula (III), which are found to be extremelypotent insect stomach poisons and systemic insecticidal agents. Thesedibenzoylhydrazines are effective for controlling a variety of insectsincluding, but not limited to Lepidoptera, Homoptera, Orthoptera,Coleoptera and Diptera, and are likewise effective for protecting avariety of crops from insect attack.

The formula (III) dibenzoylhydrazine compounds have the followingstructure: ##STR11## wherein R is C₂ -C₆ alkyl or C₅ -C₆ cycloalkyl; X,Y, M and N are each independently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br,I, nitro, CF₃ or R₁ CF₂ Z--, 1,1-difluoro-2,2-dichloroethoxy, R₂ CO orR₃ R₄ N, and when taken together, X and Y may form a ring in which XYare represented by the structure: ##STR12## and when taken together, Mand N may form a ring in which MN are represented by the structure:##STR13## Z is S(O)n or O; R₁ is H, F, CHF₂, CHFCl or CF₃ ; R₂ is C₁ -C₃alkyl, C₁ -C₃ alkoxy or R₃ R₄ N; R₃ is H or C₁ -C₃ alkyl; R₄ is H, C₁-C₃ alkyl or R₅ CO; R₅ is H or C₁ -C₃ alkyl and n is 0, 1 or 2; with theprovisos that at least one of X, Y, M or N is a substituent other thanhydrogen and when M is para nitro, at least one other of X, Y, or N mustbe a substituent other then hydrogen.

These formula (III) compounds are prepared by the reacting approximatelyequimolar amounts of a benzoic acid alkylhydrazide and a benzoyl halidein the presence of an aprotic solvent, such as an ether, chlorinatedhydrocarbon or the like and aqueous base. Generally, about two to sixmolar equivalents of base per equivalent of benzoic acid alkylhydrazideare sufficient to bring the reaction to completion. The reaction isgraphically illustrated below: ##STR14## wherein Q is halogen; and R, X,Y, M and N are as described hereinabove for formula (III).

FORMULATIONS

The formula (I) and formula (II) benzoic acid 2-alkyl- and2-cycloalkylhydrazides may be prepared and utilized as solid or liquidformulations.

In practice, protection of living plants is achieved by applying to thefoliage of said plants and/or to the soil, water or other media in whichthey are growing, about 0.1 kg/hectare to about 10.0 kg/hectare,preferably about 0.28 to 4.0 kg/hectare, of the formula (I) or formula(II) benzoic acid 2-alkyl- or 2-cycloalkylhydrazide. Advantageously,application of these formulations to the insects habitat, food supplyand/or breeding grounds at the above said rates also provide control ofinsect populations in the treated area.

If the active formula (I) or formula (II) compound is applied as adilute spray, said spray should contain 10 ppm to about 10,000 ppm ofthe active ingredient to provide the desired protection and insectcontrol.

A typical emulsifiable concentrate formulation is prepared by dispersingabout 30% w/v of the benzoic acid 1-alkyl-, 2-alkyl and2-cycloalkylhydrazide of the invention in 50% w/v of 2-pyrrolidone; in10% w/v of n-butanol; 7% w/v of a polyalkylene glycol ether, such asPOLYFAR® S320 manufactured by Westvaco-Polychemicals, CharlestonHeights, S.C.; and 3.0% w/v of nonylphenoxy polyethoxy ethanol offeredby Rohm and Haas Co as TRITON® N101.

Emulsifiable concentrates are especially useful for distributing theactive benzoic acid 1-alkyl, 2-alkyl and 2-cycloalkylhydrazides of thisinvention since they are readily dispersed in water for application asliquid sprays. Such emulsifiable concentrates also may be added toirrigation water or flooded paddies, such as used for rice cultivation,or they may be applied directly to the plants or the locus to beprotected from insect infestation using aerial applicators or groundequipment designed for ultra low volume (ULV) or low volume (LV)application of the undiluted concentrates as finely divided discretedroplets.

Granular formulations may be prepared by dissolving the active formula(I) or formula (II) hydrazide in a low-boiling solvent, such asmethylene chloride, and spraying the thus-prepared solution on asorptive carrier such as kaolin, bentonite, attapulgite, montmorilloniteor the like, in sufficient amount to provide from about 2% to 20%,preferably about 3% to 15%, by weight, of active ingredient based on thetotal weight of the granulated product.

Wettable powder formulations can be prepared by grinding together about30% to 75% by weight of the active formula (I) or (II) hydrazide withabout 5% to 10% by weight of an anionic surfactant, such as anaphthalene sulfonate condensate or a sodium or ammonium salt of acondensed mono naphthalene sulfonic acid; about 3% to 5% by weight of ananionic surfactant such as an alkyl naphthalene sulfonate, i.e. sodiumdi-n-butyl naphthalene sulfonate, sodium diisopropyl naphthalenesulfonate or the like; and the remainder of the composition an inertdiluent such as attapulgite, kaolin, montmorillonite, talc, diatomaceousearth or the like.

The following examples are presented herein simply as illustrations ofthe present invention and are not limitative thereof.

EXAMPLE 1 Preparation of benzoic acid, 2-tert-butylhydrazide

tert-Butylhydrazine hydrochloride (15.6 g, 0.125 mole) is dissolved in350 mL of methylene chloride. To this solution is added 240 mL of 10%aqueous sodium hydroxide (24 g, 0.60 mole). A solution of benzoylchloride (d=1.211, 14.5 mL, 17.6 g, 0.125 mole) in methylene chloride isthen added at moderate rate to the rapidly stirring two-phase system.

After stirring the mixture for 24 hours at ambient temperatures, themethylene chloride phase is removed, washed with 5% aqueous sodiumhydroxide, water, saturated sodium chloride solution, and then driedover sodium sulfate. Evaporation in vacuo gives 19.3 g of white solid,mp 87°-94° C., which is recrystallized from 2-propanol-water to give13.0 g of product, mp 92°-94° C.

Substituting p-chlorobenzoyl chloride for benzoyl chloride in the abovereaction yields p-chlorobenzoic acid, 2-tert-butylhydrazide; meltingpoint 116°-122° C. Similarly, substituting p-fluorobenzoyl chloride,p-nitro- benzoyl chloride, o-toluyl chloride, m-fluorobenzoyl chloride,p-bromobenzoyl chloride, p-trifluoromethylbenzoyl chloride, o-anisylchloride, p-toluyl chloride, o-chlorobenzoyl chloride, p-iodobenzoylchloride, o-iodobenzoyl chloride, p-ethylbenzoyl chloride ando-fluorobenzoyl chloride, o-nitrobenzoyl chloride, for benzoyl chloride,yields respectively: p-fluorobenzoic acid, o-bromobenzoyl chloride,2-tert-butylhydrazide; mp 136°-138° C.; p-nitrobenzoic acid,2-tert-butylhydrazide; o-toluic acid, 2-tert-butylhydrazide;m-fluorobenzoic acid, 2-tert-butylhydrazide, mp 119°-120° C.;p-bromobenzoic acid, 2-tert-butylhydrazide; p-trifluoromethylbenzoicacid, 2-tert-butylhydrazide; anisic acid, 2-tert-butylhydrazide;p-toluic acid, 2-tert-butylhydrazide; o-chlorobenzoic acid,2-tert-butylhydrazide; mp 68°-70° C.; o-iodobenzoic acid,2-tert-butylhydrazide; p-ethylbenzoic acid, 2-tert-butylhydrazide; ando-fluorobenzoic acid, 2-tert-butylhydrazide; mp 58°-59° C.;o-nitrobenzoic acid, 2-tert-butylhydrazide; mp 116°-118° C.;o-bromobenzoic acid, 2-tert-butylhydrazide; mp 85°-87° C.; andN-methylanthranilic acid, 2-tert-butylhydrazide, mp 125°-129° C.

The above reactions are illustrated below: ##STR15## wherein Q ishalogen, preferably chlorine; R is tert-butyl or tert-amyl. Othercompounds that can be prepared by the above procedure using theappropriately substituted benzoyl halide include: m-chlorobenzoic acid,2-tert-butylhydrazide, mp 120°-123° C.; p-cyanobenzoic acid,2-tert-butylhydrazide, mp 135°-136° C.; anthranilic acid,2-tert-butylhydrazide, mp 165°-167° C.; tert-butyl or isopropyl; and Xis hydrogen, halogen, C₁ -C₃ alkyl, methoxy, methylamino, NH₂, nitro orCF₃.

EXAMPLE 2 Preparation of 3,4-dichlorobenzoic acid, 2-tert-butylhydrazide

Tert-butylhydrazine hydrochloride (12.4 g, 0.1 mole) is added to asolution of sodium carbonate (23.3 g, 0.22 mole) in 100 mL of water and250 mL of ether. A solution of 3,4-dichlorobenzoyl chloride (20.9 g, 0.1mole) in 50 mL of ether is then added dropwise at 0°-15° C. After onehour, the reaction mixture is filtered and the filtrate is separated.The organic layer is washed with 100 mL of water, dried over anhydrousMgSO₄, filtered and evaporated. Recrystallization of the residue from2-propanol gives white crystals: yield 6.4 g, mp 144°-145° C.

Following the above procedure, but substituting 2,4-dichlorobenzoylchloride or 2,6-dichlorobenzoyl chloride for 3,4-dichlorobenzoylchloride, yields, respectively 2,4-dichlorobenzoic acid,2-tert-butylhydrazide, mp 115°-117° C. and 2,6-dichlorobenzoic acid,2-tert-butylhydrazide, mp 173°-174° C.

Similarly, substituting 2-chloro-4-nitrobenzoyl chloride,3-bromo-4-methylbenzoyl chloride, 2,6-difluorobenzoyl chloride,2,5-dichlorobenzoyl chloride, 3,5-dichlorobenzoyl chloride or naphthoylchloride, for 3,4-dichlorobenzoyl chloride, yields respectively:2-chloro-4-nitrobenzoic acid, 2-(tert)-butylhydrazide;3-bromo-4-methylbenzoic acid, 2-(tert)-butylhydrazide; mp 95°-97° C.;2,5-dichlorobenzoic acid, 2-(tert)-butylhydrazide and3,5-dichlorobenzoic acid, 2-(tert)-butylhydrazide, mp 163°-165° C.;1-naphthoic acid, 2-(tert)-butylhydrazide mp 148°-150° C.

These reactions are illustrated below: ##STR16## wherein Q is halogen,preferably chlorine; X and Y are each independently halogen, C₁ -C₃alkyl, methoxy, nitro or CF₃ and when taken together XY may represent##STR17##

EXAMPLE 3 Preparation of 1,2-dibenzoyl-1-tert-butylhydrazine

t-Butylhydrazine hydrochloride (101 g, 0.81 mole) is dissolved in 970 mLof 10% sodium hydroxide (97 g, 2.4 mole) in a three-liter flask withmechanical stirring. After addition of one liter of ether, the flask isfitted with a condenser and addition funnel.

Benzoyl chloride (176 mL, 213 g, 1.52 mole) in 70 mL of ether is thenadded over about a one hour period. The reaction proceeds exothermicallywith formation of a white solid. After stirring overnight, the mixtureis filtered and the resulting solids dried and then recrystallized fromisopropyl alcohol. White crystals are collected and dried and weighed togive 147.0 g of product, mp 174°-176° C.

Substituting 2,6-difluorobenzoyl chloride, 4-ethylbenzoyl chloride,4-nitrobenzoyl chloride, 4-iodobenzoyl chloride, 2-chloro-4-nitrobenzoylchloride, 3-bromo-4-toluoyl chloride, 2,5-dichlorobenzoyl chloride or3,4-(methylene-dioxy) benzoyl chloride or 3,4-naphthoyl chloride orbenzoyl chloride in the above reaction yields, respectively.1-tert-butyl-1,2-bis(2,6-difluorobenzoyl)hydrazine, mp 193°-194° C.;1-tert-butyl-1,2-bis (p-ethylbenzoyl)hydrazine, mp 178° C.;1-tert-butyl-1,2-bis (p-nitrobenzoyl)hydrazine, mp>240° C.;1-tert-butyl-1,2-bis (p-iodobenzoyl)hydrazine, mp>230° C.;1-tert-butyl-1,2-bis(2-chloro-4-nitrobenzoyl)hydrazine, mp 155°-158° C.;1-tert-butyl-1,2-bis(3-bromo-p-toluoyl)hydrazine, mp 177°-178° C.;1-tert-butyl-1,2-bis(2,5-dichlorobenzoyl)hydrazine, mp 198°-200° C.;1-tert-butyl-1,2-bis[3,4-(methylenedioxy)benzoyl]hydrazine, mp>235° C.;and 1-tert-butyl-1,2-di-2-naphthoylhydrazine, >235.

These reactions are illustrated below: ##STR18## wherein Q is halogen,preferably chlorine and X and Y are each independently hydrogen,halogen, C₁ -C₃ alkyl, methoxy, nitro, CF₃ or R₁ CF₂ Z and when takentogether X and Y may form a ring in which XY are represented by thestructure --OCH₂ O, --OCF₂ O or ##STR19## Z is S or O; R₁ is H, F, CHF₂or CF₃.

EXAMPLE 4 Preparation of2-benzoyl-1-tert-butyl-1-(3,4-dichlorobenzoyl)hydrazine

Benzoyl-2-tert-butylhydrazine (4.8 g, 0.25 mole) is stirred vigorouslyin a two-phase system of 50 mL of methylene chloride and 25 mL of 10%aqueous sodium hydroxide (2.5 g, 0.063 mole) until all dissolves. Tothis solution is added a solution of 3,4-dichlorobenzoyl chloride (7.3g, 0.025 mole) in methylene chloride. After stirring the two-phasemixture several hours at ambient temperature, the solid is removed andwashed with water and methylene chloride. Recrystallization from2-propanol gives 7.1 g (78%) of product with mp 234°-235° C.

This reaction may be illustrated as follows: ##STR20##

Following the above procedure but substituting the appropriatelysubstituted benzoyl-2-tert-butylhydrazine forbenzoyl-2-tert-butylhydrazine and the appropriately substitutedbenzoylhalide for 3,4-dichlorobenzoyl chloride yields:2-benzoyl-1-tert-butyl-1-p-toluoyl-hydrazine, mp 194°-195° C.

EXAMPLE 5 Preparation of1-benzoyl-1-tert-butyl-2-(3,4-dichlorobenzoyl)hydrazine

3,4-Dichlorobenzoyl-2-tert-butylhydrazine (5.63 g, 0.0215 mole) is addedto a rapidly stirring mixture of 40 mL of methylene chloride and 20 mLof 10% aqueous sodium hydroxide (2 g, 0.05 mole). Benzoyl chloride(d=1.211, 2.5 mL, 3.03 g, 0.0215 mole) in methylene chloride is addedand the reaction mixture stirred vigorously for approximately threehours at ambient temperature. The resulting solid is collected andwashed with water and methylene chloride.

The dried product weights 6.18 g with mp 206.5°-208.5° C.

The reaction is illustrated below: ##STR21##

Following the above procedure but substituting the appropriatelysubstituted benzoyl-2-tert-butylhydrazine for3,4-dichlorobenzoyl-2-tert-butylhydrazine and the appropriatelysubstituted benzoyl chloride for benzoyl chloride yields the followingcompounds: 1-tert-butyl-2-(p-chlorobenzoyl)-1-p-toluoylhydrazine, mp223.5°-224.0° C.;1-p-anisoyl-1-tert-butyl-2-(3,4-dichlorobenzoyl)hydrazine, mp >230° C.;1-tert-butyl-2-(3,4-dichlorobenzoyl)-1-o-toluoylhydrazine, mp 133°-136°C.; 1-tert-butyl-2-(3,4-dichlorobenzoyl)-1-(p-nitrobenzoyl)hydrazine,mp >230° C.; 1-tertbutyl-2-(3,4-dichlorobenzoyl)-1-(α, α,α-trifluoro-p-toluoyl)hydrazine, mp 212°-213° C.; and1-tert-butyl-2-(3,4-dichlorobenzoyl-1-(α, α,α-trifluoro-o-toluoyl)hydrazine, mp 171°-172.5° C.

EXAMPLE 6 Preparation of benzoic acid,3,4-dichloroisopropylidenehydrazine

3,4-Dichlorobenzoic acid hydrazide (11.7 g, 0.060 mole) is placed in thethimble of a Soxhlet extractor and flooded with hot acetone from anattached distillation flask. After overnight reflux, the acetone mixtureconcentrated under vacuum to afford a white solid. Recrystallizationfrom ethyl acetate petroleum ether gives 9.5 g of the title compound aswhite crystals, mp 141°-144° C.

This reaction is illustrated as below: ##STR22##

Following the above procedure but substituting the appropriate aldehydeor ketone for acetone yields the following compounds: benzoic acid(1-ethylpropylidene)hydrazide, mp 89°-91° C.; and benzoic acid(2,2-dimethylpropylidene)hydrazide, mp 168°-169° C.

EXAMPLE 7 Preparation of 3,4-dichlorobenzoic acid, 2-isopropylhydrazide

3,4-Dichlorobenzoic acid isopropylidenehydrazide (9.2 g, 0.040 mole) and100 mg of platinum oxide in 100 mL of methanol in a Parr hydrogenationapparatus is shaken for one hour and 30 minutes under an initialhydrogen pressure of 40 psig. The filtered reaction mixture isconcentrated under vacuum and the resulting solids are recrystallizedthree times from isopropyl alcohol to give 2.6 g of the title compoundas a white crystalline product, mp 112.5°-115° C.

The reaction is illustrated below: ##STR23##

EXAMPLE 8 Preparation of1-benzoyl-2-(3,4-dichlorobenzoyl)-1-isopropylhydrazine

A mixture of 3,4-dichlorobenzoic acid, 2-isopropylhydrazide (0.98 g,0.004 mole) and benzoyl chloride (0.56 g, 0.004 mole) is stirredovernight in 1.2 mL of ethylene dichloride and 6.5 mL of 10% sodiumhydroxide. The organic phase is removed and the aqueous mixture isextracted with 25 mL of ethylene dichloride. The organic extracts arecombined and concentrated to a yellow oil which is taken up in hotisopropyl alcohol. Cooling the alcohol solution causes precipitation ofthe title compound as a white crystalline product, which is collected byfiltration and has a mp of 157° C.

Following one or more of the procedures described in examples 1-8 aboveyields the compounds listed in Table I below. The reactions isgraphically illustrated below. ##STR24##

                                      TABLE I                                     __________________________________________________________________________    Compounds having the structure                                                R        X     Y      M     N      mp °C.                              __________________________________________________________________________    C(CH.sub.3).sub.3                                                                      H     4Cl    H     4Cl    >240                                       C(CH.sub.3).sub.3                                                                      3Cl   4Cl    3Cl   4Cl    228.0-229.0                                C(CH.sub.3).sub.3                                                                      2CH.sub.3                                                                           H      2CH.sub.3                                                                           H      196.0-197.0                                C(CH.sub.3).sub.3                                                                      2Cl   4Cl    2Cl   4Cl    115.0-117.0                                C(CH.sub.3).sub.3                                                                      H     4CF.sub.3                                                                            H     4CF.sub.3                                                                            226.0-227.0                                C(CH.sub.3).sub.3                                                                      H     4OCH.sub.3                                                                           H     4OCH.sub.3                                                                           119.0-201.0                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     H      206.5-208.5                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4Cl    >240                                       C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4CN     230                                       C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4OCH.sub.3                                                                           >230                                       C(CH.sub.3).sub.3                                                                      CHCHCHCH     CHCHCHCH     182.0-183.0                                         (2,3)        (2,3)        α-naphthyl                           C(CH.sub.3).sub.3                                                                      3Cl   4Cl    2CH.sub.3                                                                           H      133.0-136.0                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     SO.sub.2 CH.sub.3                                                                    237.0-240.0                                CH(CH.sub.3).sub.2                                                                     3Cl   4Cl    3Cl   4Cl    154.0-156.0                                C(CH.sub.3).sub.3                                                                      4Br   H      4Br   H      219.0-220.0                                C(CH.sub.3).sub.3                                                                      H     4F     H     4F     196.0-198.0                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4NO.sub.2                                                                            >230                                       C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4CF.sub.3                                                                            212.0-213.0                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    H     4CH.sub.3                                                                            225.5-227.0                                C(CH.sub.3).sub.3                                                                      H     H      3Cl   4Cl    234.0-235.5                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    2F    6F     195.0-197.0                                CH(CH.sub.3).sub.2                                                                     3Cl   4Cl    H     H      163.0-164.5                                C(CH.sub.3).sub.3                                                                      H     4CH.sub.3                                                                            H     4CH.sub.3                                                                            218.0-219.0                                C(CH.sub.3).sub.3                                                                      H     4Cl    3Cl   4Cl    190.0-192.0                                C(CH.sub.3).sub.3                                                                      2F    H      2F    H      135.0-137.0                                C(CH.sub.3).sub.3                                                                      3Cl   4Cl    2CF.sub.3                                                                           H      171.0-172.5                                C(CH.sub.3).sub.3                                                                      3Cl   H      3Cl   H      205.0-206.0                                C(CH.sub.3).sub.3                                                                      H     2Cl    H     2Cl    222.0-223.0                                C(CH.sub.3).sub.3                                                                      2F    6F     2F    6F     236.0                                      C(CH.sub. 3).sub.3                                                                     OCH.sub.2 O-(3,4)                                                                          OCH.sub.2 O-(3,4)                                                                          220.0-221.0                                C(CH.sub.3).sub.3                                                                      2Cl   4NO.sub.2                                                                            2Cl   4NO.sub.2                                                                            155.0-158.0                                CH(C.sub.2 H.sub.5).sub.2                                                              H     H      H     H      199.0-201.0                                C(CH.sub.3).sub.3                                                                      3Cl   5Cl    3Cl   5Cl    219.0-221.0                                C(CH.sub.3).sub.3                                                                      H     2CF.sub.3                                                                            H     2CF.sub.3                                                                            211.0                                      C(CH.sub.3).sub.3                                                                      H     3CH.sub.3                                                                            H     3CH.sub.3                                                                            152.0-153.0                                 ##STR25##                                                                             H     H      H     H      194.0-197.0                                 -n-C.sub.4 H.sub.9                                                                    H     H      H     H      106.0-108.0                                 ##STR26##                                                                             H     H      H     H      185.0-188.0                                C(CH.sub.3).sub.3                                                                      CHCHCHCH     CHCHCHCH     >235                                                (3,4)        (3,4)                                                   C(CH.sub.3).sub.3                                                                      H     4C.sub.2 H.sub.5                                                                     H     4C.sub.2 H.sub.5                                                                     178.0                                      C(CH.sub.3).sub.3                                                                      3Br   4CH.sub.3                                                                            3Br   4CH.sub.3                                                                            177.0-178.0                                C(CH.sub.3).sub.3                                                                      4Cl   H      4CH.sub.3                                                                           H      223.0-224.0                                C(CH.sub.3).sub.3                                                                      H     H      4CH.sub.3                                                                           H      194.0-195.0                                C(CH.sub. 3).sub.3                                                                     H     4NO.sub.2                                                                            H     4NO.sub.2                                                                            >240.0                                     C(CH.sub.3).sub.3                                                                      H     4I     H     4I     >230.0                                     C(CH.sub.3).sub.3                                                                      2Cl   5Cl    2Cl   5Cl    199.0-200.0                                C(CH.sub.3).sub.3                                                                      2I    H      2I    H      206.0-207.0                                C(CH.sub.3).sub.3                                                                      2Cl   H      H     4F     >250.0                                     CH(CH.sub.3).sub.2                                                                     H     H      H     H                                                 __________________________________________________________________________

EXAMPLE 9 Preparation of acetone tert-butylhydrazone

To 6.6 g of acetone, cooled in an ice bath, is added 5.0 g oftert-butylhydrazine. The mixture is stirred and then allowed to standfor several minutes. Ether and potassium hydroxide pellets are thenadded to the mixture. The mixture is stirred, and then the ethereallayer is separated from the mixture. Distillation of the ethereal layeryields the product acetone tert-butylhydrazone b.p. 132°-134° C.

The reaction is illustrated as follows: ##STR27##

EXAMPLE 10 Preparation of 1-tert-butyl-2-isopropylidenehydrazide ofbenzoic acid

Acetone tert-butylhydrazone (2.0 g) is admixed with 4.4 g of benzoylchloride and 15 mL of 10% sodium hydroxide. The mixture is stirred untilthe benzoyl chloride odor is no longer detectable. The resulting productis then dissolved in ether and dried over magnesium sulfate. Evaporationof the solvent from the mixture leaves acetoneN-tert-butyl-N-benzoylhydrazone, b.p. 100°-103° C. This product also isreferred to as 1-tert-butyl-2-isopropylidenehydrazide of benzoic acid.

Following the above procedure, but substituting p-chlorobenzoyl chloridefor benzoyl chloride yields the product1-tert-butyl-2-isopropylidenehydrazide of p-chlorobenzoic acid.

Substitution of the o-nitrobenzoyl chloride or o-fluorobenzoyl chloridefor benzoyl chloride in the above procedure yields, respectively,1-tert-butyl-2-isopropylidenehydrazide of o-nitrobenzoic acid and1-tert-butyl-2-isopropylidenehydrazide of p-fluorobenzoic acid. Thereactions are illustrated as follows: ##STR28##

EXAMPLE 11 Preparation of benzoic acid, 1-tert-butylhydrazide

A solution of 0.5 g of the 1-tert-butyl-2-isopropylidenehydrazide ofbenzoic acid, 3 mL of 10% hydrochloric acid and 3 mL of methanol ismixed and allowed to stand for 12 hours. The mixture is made basic withdilute sodium hydroxide. The methanol is evaporated from the mixtureyielding the product 1-tert-butylhydrazide of benzoic acid, m.p.117°-123° C.

The above procedure is used, but 1-tert-butyl-2-isopropylidenehydrazideof p-chlorobenzoic acid is substituted for1-tert-butyl-2-isopropylidenehydrazide of benzoic acid. This yields1-tert-butylhydrazide of p-chlorobenzoic acid, m.p. 134°-136° C.

Similarly, 1-tert-butylhydrazide o-nitrobenzoic acid, m.p. 141°-144° C.and 1-tert-butylhydrazide of p-fluorobenzoic acid, m.p. 136°-137° C.; isprepared by the above reaction using the appropriately substitutedbenzoic acid, 1-tert-butyl-2-isopropylidenehydrazide. The reactions areillustrated as follows: ##STR29##

EXAMPLE 12 Insecticidal activity of the compounds of the invention

The compounds of the present invention exhibit insecticidal activityagainst a variety of insects at various concentrations of activeingredient in acetone-water solutions. As illustrative of thisinsecticidal activity is control of Spodoptera eridania (third-instarlarvae, southern armyworm), Spodoptera eridania (seven-day residual),Spodoptera eridania (third-instar cut-stem systemic test, southernarmyworm), Anopheles quadrimaculatus (adults, common malaria mosquito),Heliothis virescens (third-instar tobacco budworm), Blattella germanica(residue test, adult male German cockroach), and Leptinotarsadecemlineata (Colorado potato beetles).

Further, systemic activity of the compounds is observed when tested forcontrolling Colorado potato beetles (Leptinotarsa decemlineata) onpotato plants, (Solanum tuberosum). These beetles are resistant tocarbamates, phosphates and pyrethroids but are controlled by the presentcompounds.

Bean plants, Phaseolus limensis, also are protected from southernarmyworms, Spodoptera eridania and systemically protected from potatoleafhoppers, Empoasca abrupta.

Maize plants (Zea mays L. plants) also are protected from insect attackof southern armyworm larvae (Spodoptera eridania, third-instar larvae,southern armyworm) and systemically from southern corn rootworm(Diabrotical undecimpunctata howardi).

Rice plants, Oryza sativa, are protected via systemic application, aswell as by foliar application, from armyworms, Spodoptera frugiperda,and leafhoppers, Empoasca abrupta.

Cotton plants Gossypium hirsutum, also are systemically protected, aswell as by foliar application from tobacco budworms (Heliotrisvirescens).

What is claimed is:
 1. A compound having the structural formula:##STR30## wherein R is hydrogen; R₆ is tert-butyl; X and Y are eachindependently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF₃, R₁CF₂ Z--, 1,1-difluoro-2,2-dichloroethoxy, R₂ CO or R₃ R₄ N; Z isS(O)_(n) or O; R₁ is H, F, CHF₂, CHFCl or CF₃ ; R₂ is C₁ -C₃ alkyl, C₁-C₃ alkoxy or R₃ R₄ N; R₃ is H or C₁ -C₃ alkyl; R₄ is H, C₁ -C₃ alkyl orR₅ CO; R₅ is H or C₁ -C₃ alkyl and n is 0, 1 or 2; with the proviso thatat least one of X and Y is a substituent other than hydrogen.
 2. Thecompound according to claim 1, wherein said compound is p-fluorobenzoicacid 1-tert-butylhydrazide.
 3. The compound according to claim 1 whichis p-chlorobenzoic acid 1-tert-butyl hydrazide.
 4. The compoundaccording to claim 1 which is o-nitrobenzoic acid 1-tert-butylhydrazide.